CN1019959C - 具有聚(4-甲基-1-戊烯)底层的层合薄膜 - Google Patents
具有聚(4-甲基-1-戊烯)底层的层合薄膜 Download PDFInfo
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Abstract
本发明公开了一种层合薄膜,该薄膜含(A)基于4-甲基-1-戊烯的聚合物的底层;(B)α-烯烃共聚物(含10~85摩尔%的丙烯,3~60摩尔%的1-丁烯和10~85摩尔%具有5个或更多碳原子的α-烯烃)的夹层,该夹层层合在上述底层的至少一个面上,上述共聚物的结晶度用X-射线衍射法测定为20%或更低;(C)贴合在夹层上的α-烯烃聚合物材料的可热合层,上述聚合物主要含具有2~4个碳原子的α-烯烃。
Description
本发明涉及具有高的可热合性且含聚(4-甲基-1-戊烯)基质的层合薄膜。
由于聚(4-甲基-1-戊烯)具有好的透明性,耐热性、耐化学性等,已被用作实验器皿,例如烧杯或量筒、注射器、光学测量仪所用的测定池、微波炉所用的托盘、含其涂覆纸的烘烤箱等。虽然聚(4-甲基-1-戊烯)具有高的熔点和好的耐热性,但其缺点在干可热合性差。改进这种可热合性最常用的方法是用可热合性好且熔点低的一种树脂(例如聚乙烯或聚丙烯)层合聚(4-甲基-1-戊烯)。虽然聚(4-甲基-1-戊烯)和聚乙烯或聚丙烯都是聚烯烃,但它们不能互相粘合。因此,通过层合这些薄层生产的产品实际上不能使用。
另外,如果采用涂覆一层主要是聚氨酯的粘合剂作为粘合涂覆剂的方法使聚(4-甲基-1-戊烯)薄膜层合在聚乙烯薄膜上,其可热合性不会大大地改善,这是因为聚(4-甲基-1-戊烯)薄膜的表明润湿性差,因此,得到的层合薄膜的粘合强度低。
本专利申请的受让人已递交过一份日本专利申请No59-1387(未审公告No60-145844),该申请公开了一种具有改进的粘合强度和高的可热合性的层合薄膜,其生成方法可以是使用一种特殊的丙烯和α-烯烃的无规共聚物作为层合聚(4-甲基-1-戊烯)薄膜和聚乙烯或聚丙烯薄膜的粘合层。
本申请的发明人现已发现,通过使用与本申请相同的受让人递交的日本未审专利公告No60-166310所公开的特殊的α-烯烃共聚物作为粘合层的方法可使含聚(4-甲基-1-戊烯)底层的层合薄膜的粘合强度进一步得到提高。
因此,本发明的目的是提供一种改进的层合薄膜,该薄膜包括:
(A)基于4-甲基-1-戊烯的聚合物的底层;
(B)α-烯烃共聚物(含10~85摩尔%的丙烯,3~60摩尔%的1-丁烯和10~85摩尔%具有5个或更多碳原子的α-烯烃)的夹层,该夹层层合在上述底层的至少一个面上,上述共聚物的结晶度用X-射线衍射法测定为20%或更低,特性粘度〔η〕(在萘烷中和135℃下测得)为0.6至5分升/克,不溶于沸腾的正庚烷的物质为5.0%(重量)或更低,并且在25℃不溶于丙酮的物质为5.0%(重量)或更低。
(C)α-烯烃聚合物材料的可热合层,该可热合层贴合在夹层上,上述聚合物主要含具有2至4个碳原子的α-烯烃。
本发明的其它目的和优点可从下列具体描述明显看出。
构成底层(A)的聚合物可以4-甲基-1-戊烯的均聚物或通常含85摩尔%或更多的4-甲基-1-戊烯和15摩尔%或更少的其它具有2至20个碳原子的α-烯烃(如乙烯、丙烯、1-丁烯、1-己烯、1-辛烯、1-癸烯、1-十四碳烯、1-十八碳烯等)的共聚物;基于4-甲基-1-戊烯的聚合物的熔体流速(MFR5;负载5公斤;260℃)宜为0.5至200克/10分钟。熔体流速低于0.5克/10分钟的聚合物具有高的熔体粘度,因此模塑性差;相反,熔体流速大于200克/10分钟的聚合物具有低的熔体粘度,因此模塑性差且机械强度低。
构成夹层(B)的α-烯烃共聚物含10~85摩尔%,较好的为15~70摩尔%,更好的为25~55摩尔%的丙烯;3-60摩尔%,较好的为5~50摩尔%,更好的为10~40摩尔%的1-丁烯和10~85摩尔%,较好的为15~70摩尔%更好的为20~60摩尔%的α-烯烃,该烯烃具有5个或更多,较好的为6~12个碳原子。用X光衍射法测得该共聚物的结晶度为20%或更低,较好的为15%或更低,更好的为10%或更低。具有5个或更多碳原子的α-烯烃的例子可以是1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-庚烯、1-辛烯、1-癸烯、1-十二碳烯等。
当α-烯烃共聚物中丙烯的含量低于10摩尔%或高于85摩尔%,1-丁
烯的含量低于3摩尔%或高于60摩尔%,或α-烯烃的含量低于10摩尔%或高于85摩尔%时,对底层(A)的粘合强度会减弱。另外,用X-射线衍射法测得的结晶度高于20%的α-烯烃共聚物对底层(A)的粘合性也低。
在本发明中,用X-射线衍射法测定α-烯烃共聚物的结晶度的方法如下所述:
将试样在280℃、30公斤/厘米2的条件下模塑10分钟,在水冷压机中(压力30千克/厘米2)在23℃下冷却5分钟,然后模制试样。用装有旋转阳极和铜靶的X-射线衍射仪(RU-300;Rigaku Denki K.K.)在5°~31°的衍射角(2θ)下测定试样的X-射线衍射曲线。在6°和30°之间描制一根基线以划分非结晶部分和结晶部分,根据重量百分率确定结晶部分。
构成本发明所用的夹层(B)的α-烯烃共聚物的特性粘度[η](在萘烷中和135℃下测量)为0.5至6分升/克,较好的为0.6至5分升/克,更好的为1.0至4分升/克。特性粘度在这范围之外的α-烯烃共聚物显示出低的模塑性。
就夹层(B)的α-烯烃共聚物而言,较好的是不溶于沸腾的正庚烷的物质为5.0%(重量)或更低,而在25℃溶于丙酮的物质为5.0%(重量)或更低;更好的是不溶于沸腾的正庚烷的物质为4.0%(重量)或更低,而在25℃溶于丙酮的物质为2.5%(重量)或更低。若不溶于沸腾的正庚烷的物质多于5%(重量),则α-烯烃共聚物的透明度降低,或在模塑的薄膜中出现诸如鱼眼之类的缺限。若溶于丙酮的物质多于3.0%(重量),则共聚物薄膜的表面变粘,则会降低对底层(A)的粘合性。
在本发明中,有关α烯烃共聚物中不溶于沸腾的正庚烷的物质和在25℃溶于丙酮的物质的含量按下述方法测定:
将小样品(约1毫米×1毫米×1毫米)和玻璃珠一起加入柱式玻璃
过滤器中并在索格利特抽提器中抽提14小时,称量可溶或不溶成分后,计算不溶物质的重量百分率,这样即可测定不溶于正庚烷的物质。
将15克试样在130℃溶于250毫升正癸烷中,所得的溶液倒入500毫升丙酮中,不溶于丙酮的聚合物发生沉淀,过滤收集滤液,往滤液中加入300毫升水,用分液漏斗把正癸烷层与水-丙酮层分离开,浓缩正癸烷层,这样即可测定在25℃溶于丙酮的物质。
具有上述比例且可用于本发明的夹层(B)的α-烯烃共聚物可通过使用一种催化剂由丙烯、1-丁烯和α-烯烃无规共聚制得,上述催化剂包含:
(ⅰ)固态钛催化剂组分,该组分可由(b)一种囟化烃处理(a)含镁化合物、钛化合物和电子给体的高活性固态钛催化剂组分的方法制得;
(ⅱ)有机铝化合物组分;和
(ⅲ)含硅化合物的电子给体组分。
生产该催化剂的方法在例如日本未审专利公告No56-811和No58-83006中有所描述,这些公开内容作为参考并入本发明。另外,夹层(B)的α-烯烃共聚物的聚合条件在例如日本未审专利公告No60-166310中有所描述,该公开内容作为参考并入本发明。
构成可热合层(c)的α-烯烃聚合物材料可以是主要含乙烯、丙烯或1-丁烯的结晶聚合物。具体地说,α-烯烃聚合物材料可以是乙烯、丙烯或1-丁烯的均聚物;乙烯、丙烯或1-丁烯与少量其它具有2~20碳原子的α-烯烃或乙烯基化合物(如乙酸乙烯酯、氯乙烯、丙烯酸、甲基丙烯酸或苯乙烯)的共聚物;用不饱和羧酸或其衍生物(如马来酐、马来酸或丙烯酸)改性的其接枝共聚物;或其混合物。
作为α-烯烃聚合物材料的例子的聚乙烯类包括高压低密度聚乙烯(简称LDPE)、乙烯/丙烯共聚物、乙烯/1-丁烯共聚物、乙烯/4-甲基-1-戊烯共聚物、乙烯/1-己烯共聚物、高密度聚乙烯(简称
HDPE)、乙烯/乙酸乙烯酯共聚物、乙烯/丙烯酸共聚物等。由于LDPE、乙烯/α-烯烃共聚物和乙烯/乙酸乙烯酯共聚物的透明性和低温热合性好,因此它们是优选的。在上述聚乙烯类中,密度为0.910-0.960且熔点(Tm:ASTM D3418)为100至135℃的那些聚乙烯类是最好的。另外,尽管这些聚乙烯类的熔体流速(MFR3:ASTM D1238,E)不受限制,但考虑到其模塑性,其熔体流速宜为0.01至30克/10分钟,更好的为0.1至10克/10分钟。
作为α-烯烃聚合材料的例子,优选的聚丙烯类包括:聚丙烯(丙烯均聚物);通常含90摩尔%或更多,较好的为95摩尔%或更多丙烯的丙烯无规共聚物,例如,丙烯/乙烯无规共聚物、丙烯/乙烯/1-丁烯无规共聚物、丙烯/1-丁烯无规共聚物;或通常含5至30摩尔%乙烯的丙烯/乙烯嵌段共聚物。由于均聚物和无规共聚物的透明性好,因而是优选的。从可热合性好的角度考虑,最好是熔点(Tm:ASTM D3418)为130至140℃的无规共聚物。虽然所述共聚物的熔体流速不受限制,但考虑到模塑性,其熔体流速宜为0.5至30克/10分钟,更好的为0.5至10克/10分钟。
作为α-烯烃聚合物材料的例子,优选的聚1-丁烯包括1-丁烯均聚物、1-丁烯/乙烯共聚物、1-丁烯/丙烯共聚物或1-丁烯/4-甲基-1-戊烯共聚物。虽然这类聚合物的熔体流速(MFR3:ASTM D1238,E)不受限制,但考虑模塑性,其熔体流速宜为0.01至100克/10分钟,更好的为0.03至30克/10分钟。
本发明的层合薄膜包括基于4-甲基-1-戊烯的聚合物的底层(A);层合在底层(A)的至少一面上的α-烯烃共聚物的夹层(B);和层合在夹层(B)上的α-烯烃聚合物材料的可热合层(C)。
本发明的层合薄膜可用各种已知的方法生产;例如,一种方法是先模塑基于4-甲基-1-戊烯的聚合物的薄膜,然后在其上挤压涂覆α-烯烃共
聚物和α-烯烃聚合材料;一种先模塑基于4-甲基-1-戊烯的聚合物的薄膜,然后将α-烯烃共聚物与α-烯烃聚合材料的薄膜一起挤压叠合的方法;或一种通过具有多层结构(至少三层)的多层模口,以α-烯烃共聚物作夹层,共挤出基于4-甲基-1-戊烯的聚合物、α-烯烃共聚物和α-烯烃聚合物材料的方法。由于共挤出法操作简单且能生产各层之间粘合得好的层合薄膜,因此该方法是优选的。两种典型的共挤压法即使用扁平模头的T型塑模法和使用环型模头的吹胀法是已知的。作为扁平模头,既可使用采用一个黑盒的单料道式,也可使用多料道式;任何已知的模头都可用作吹胀模头。
本发明的层合薄膜中各层的厚度不受限制。但底层(A)的厚度宜为10~100微米,更好的为10~50微米,夹层(B)的厚度宜为5~50微米,更好的为10~30微米,可热合层(C)的厚度宜为10~100微米,更好的为10~50微米。
任何具有基于4-甲基-1-戊烯的聚合物底层(A)、α-烯烃共聚物的夹层(B)和α-烯烃聚合物材料的可热合层(C)的层合薄膜都在本发明的范围内,因此,本发明的层合薄膜包括借助于夹层(B)在底层(A)的两面都载有可热合层(C)而形成的薄膜。另外,本发明的层合薄膜还可在其上载有阻气层,该阻气层含基于聚二氯乙烯、聚乙烯醇、乙烯/乙酸乙烯酯的皂化共聚物、聚酰胺、聚酯的树脂、纸或铝箔等。
在所有构成本发明的层合薄膜的底层(A)、夹层(B)和可热合层(C)中,可掺入各种常用于聚烯烃的添加剂,如抗老化剂、热稳定剂、抗静电剂、防雾剂、防粘剂、滑脱剂、润滑剂、颜料,着色剂、抗粘剂、成核剂等,其条件是这种掺合不违背本发明的目的。在可热合层(C)中可掺入具有微结晶或无结晶性质的乙烯/α-烯烃共聚物,如乙烯/丙烯共聚物或乙烯/1-丁烯共聚物、或乙烯/乙酸乙烯酯共聚物等,以提高可热合性。
由于本发明的层合薄膜因含聚(4-甲基-1-戊烯)而不仅具有好的耐热性、透明度、表面光泽、拒水性等,而且具有好的可热合性,因而宜用作各种食品(如蔬菜、糖果、肉类、面包或海货)的包装材料。
本发明将通过下列实施例作进一步的说明,但并不意味着限于这些实施例。
实施例1
将4-甲基-1-戊烯/1-癸烯共聚物(密度:0.835克/厘米3,MFR5:26克/10分钟)(下文称为“MP-I”)、丙烯/1-丁烯/4-甲基-1-戊烯(丙烯含量:36摩尔%,1-丁烯含量:14摩尔%,4-甲基-1-戊烯含量:50摩尔%,玻璃化转变温度(Tg):5℃,密度(D):0.860克/厘米3,MFR:0.88克/10分钟,X-射线衍射法测得的结晶度:1.2%)(下文称为“PBM-I”)和高压聚乙烯(熔点(Tm):105℃)(下文称为“LDPE-I”)分别装入料筒温度为270℃的40毫米直径挤塑机、料筒温度为250℃的40毫米直径挤塑机和料筒温度为250℃的40毫米直径挤塑机中熔融,用PBM-I作为夹层,通过三层T-模薄膜挤塑机的衣架型模头(模头温度:260℃)进行挤塑并冷却,获得共挤出的三层薄膜,4MD-I层厚度为30微米,PBM-I层厚度为20微米,LDPE-I层厚度为30微米。其性质能按下列方法测量:
粘合强度(克/15毫米)
切割一宽15毫米的试样,以不超过200毫米/分钟的剥离速度把样品剥离成二层。记录各层剥离速度下的强度。
热合部位的剥离强度(克/15毫米)
将一层合薄膜放在另一层合薄膜上,其放置式是使这两块层合薄膜的可热合层(C)互相接触。在120℃或170℃以及2公斤/厘米2的压力下用银棒(宽10毫米)热合1秒钟,然后使其冷却。切割宽15毫米的样品,
以不超过200毫米/分钟的剥离速度剥离样品的热合部位。记录热合部位剥离速度下的强度。
结果列于表1中。
实施例2
重复上述实施例1的步骤,不同之处在于用丙烯/1-丁烯/4-甲基-1-戊烯共聚物(丙烯含量:46摩尔%,1-丁烯含量:18摩尔%,4-甲基-1-戊烯含量:36摩尔%,玻璃化转变温度(Tg):23℃,密度(D):0.847克/厘米3,MFR:1.2克/10分钟,用X-射线衍射法测得的结晶度为4.3%)(下文称为“PBM-Ⅱ”)代替PBM-Ⅰ作为夹层。结果列于表1中。
实施例3
重复上述实施例1的步骤,不同之处在于用丙烯/1-丁烯/4-甲基-1-戊烯共聚物(丙烯含量:44摩尔%,1-丁烯含量:28摩尔%,4-甲基-1-戊烯含量:28摩尔%,玻璃化转变温度(Tg):170℃,密度(D):0.851克/厘米3,MFR:1.5克/10分钟,用X-射线衍射法测得的结晶度:3.3%)(下文称为“PBM-Ⅲ”)代替PBM-Ⅰ作为夹层。结果列于表1中。
实施例4
重复上述实施例1的步骤,不同之处在于用丙烯/乙烯无规共聚物(密度:0.91克/厘米3,MFR:5克/10分钟,Tm:140℃)(下文称为“PP-Ⅰ”)代替LDPE-1,“PP-Ⅰ”所用的挤塑机的料筒温度为270℃。结果列于表1中。
对比实施例1
重复上述实施例1的步骤,不同之处在于用丙烯/1-丁烯无规共聚物(丙烯含量:71摩尔%,熔点:110℃,MFR:7.0克/10分钟)(下文称为“PBR-Ⅰ”)代替“PBM-Ⅰ”作为夹层。结果列于表1中。
虽然本发明已参照具体实施方案作了描述,但本领域熟练技术人员所做的任何明显的变更和修改都认为是落在本发明的范围内。
Claims (6)
1、一种层合薄膜,该薄膜包含:
(A)基于4-甲基-1-戊烯的聚合物的底层;
(B)α-烯烃共聚物(含10~85摩尔%的丙烯,3~60摩尔%的1-丁烯和10~85摩尔%具有5个或更多碳原子的α-烯烃)的夹层,该夹层层合在上述底层的至少一个面上,上述共聚物的结晶度用X-射线衍射法测定为20%或更低,特性粘度[η](在萘烷中和135℃下测得)为0.6至5分升/克,不溶于沸腾的正庚烷的物质为5.0%(重量)或更低,并且在25℃不溶于丙酮的物质为5.0%(重量)或更低;
(C)α-烯烃聚合物材料的可热合层,该可热合层贴合在夹层上,上述聚合物主要含具有2至4个碳原子的α-烯烃。
2、根据权利要求1所述的层合薄膜,其中构成底层的聚合物含85摩尔%或更多的4-甲基-1-戊烯和15摩尔%或更少的具有2至20个碳原子的其它α-烯烃。
3、根据权利要求1所述的层合薄膜,其中构成夹层的α-烯烃共聚物含15~70摩尔%丙烯、5~50摩尔%1-丁烯和15~70摩尔%具有5个或更多碳原子的α-烯烃,共聚物的结晶度为15%或更低。
4、根据权利要求3所述的层合薄膜,其中具有5个或更多碳原子的α-烯烃选自1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、3-甲基-1-戊烯、1-庚烯、1-辛烯、1-癸烯和1-十二碳烯。
5、根据权利要求1所述的层合薄膜,其中构成可热合层的α-烯烃聚合物材料选自乙烯、丙烯或1-丁烯的均聚物;乙烯、丙烯或1-丁烯与少量其它具有2~20个碳原子的α-烯烃或乙烯基化合物的共聚物;用不饱和羧酸或其衍生物改性的其接枝共聚物;及其混合物。
6、根据权利要求1所述的层合薄膜,该薄膜还含有阻气层。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP62130012A JPH0729405B2 (ja) | 1987-05-28 | 1987-05-28 | 積層フイルム |
JP130012/87 | 1987-05-28 |
Publications (2)
Publication Number | Publication Date |
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CN88103178A CN88103178A (zh) | 1988-12-28 |
CN1019959C true CN1019959C (zh) | 1993-03-03 |
Family
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Application Number | Title | Priority Date | Filing Date |
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CN88103178A Expired - Fee Related CN1019959C (zh) | 1987-05-28 | 1988-05-28 | 具有聚(4-甲基-1-戊烯)底层的层合薄膜 |
Country Status (10)
Country | Link |
---|---|
US (1) | US5077123A (zh) |
EP (1) | EP0293187B1 (zh) |
JP (1) | JPH0729405B2 (zh) |
KR (1) | KR950012794B1 (zh) |
CN (1) | CN1019959C (zh) |
AT (1) | ATE84748T1 (zh) |
AU (1) | AU606419B2 (zh) |
CA (1) | CA1311998C (zh) |
DE (1) | DE3877624T2 (zh) |
NZ (1) | NZ224818A (zh) |
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CA2014460C (en) * | 1989-04-17 | 2001-02-27 | Hiromi Shigemoto | Laminated film or sheet and box-shaped vessel prepared therefrom |
US5693418A (en) * | 1989-04-17 | 1997-12-02 | Mitsui Petrochemical Industries, Ltd. | Laminated film or sheet and box-shaped vessel prepared therefrom |
IT1245741B (it) * | 1990-11-16 | 1994-10-14 | Grace W R & Co | Contenitori multistrato con resistenza a trattamenti termici migliorata |
DE69308385T2 (de) * | 1992-05-20 | 1997-07-10 | Mitsui Petrochemical Ind | Kunststoffzusammensetzung |
US5484654A (en) * | 1993-03-12 | 1996-01-16 | W.R. Grace & Co. | Packaging material and method of making a packaging material |
US5336721A (en) * | 1993-04-06 | 1994-08-09 | Quantum Chemical Corporation | Adhesive blends of ethylene-alkyl acrylate copolymers and modified propylene-ethylene copolymers |
DE4419709A1 (de) * | 1994-06-06 | 1995-12-07 | Wolff Walsrode Ag | Gasundurchlässige, hochtransparente und durchstichfeste Verbundfolie |
EP0686500A3 (de) * | 1994-06-06 | 1998-05-13 | Wolff Walsrode Ag | Verbundfolie enthaltend auf der Siegelseite zwei Propylen-Copolymerisat-Schichten |
JP2978086B2 (ja) * | 1995-06-30 | 1999-11-15 | 住友ベークライト株式会社 | 積層体 |
EP0943427A4 (en) * | 1997-08-22 | 2001-10-17 | Mitsui Chemicals Inc | MULTILAYER FILMS CONTAINING POLY (4-METHYL-1-PENTEN) AND THEIR USE |
CN1269881C (zh) * | 1999-09-07 | 2006-08-16 | 纳幕尔杜邦公司 | 可热封聚烯烃及由其制成的制品 |
MXPA03005627A (es) * | 2000-12-22 | 2004-12-03 | Exxonmobil Chem Patents Inc | Estructura polimerica compuesta. |
JP5069856B2 (ja) * | 2005-12-14 | 2012-11-07 | 三井化学ファブロ株式会社 | 食品包装用フィルム |
US20080311364A1 (en) * | 2007-06-15 | 2008-12-18 | Sanchez Jose De Jesus Ortega | Multi-layered self-adhesive protective film |
WO2013099876A1 (ja) | 2011-12-27 | 2013-07-04 | 三井化学株式会社 | 4-メチル-1-ペンテン(共)重合体組成物、該組成物からなるフィルムおよび中空成形体 |
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US4105118A (en) * | 1976-06-10 | 1978-08-08 | Eastman Kodak Company | Laminates useful as packaging materials and container having alkaline fluid means |
JPS55132244A (en) * | 1979-04-02 | 1980-10-14 | Mitsubishi Petrochemical Co | Laminating material |
JPS6063243A (ja) * | 1983-09-19 | 1985-04-11 | Mitsui Petrochem Ind Ltd | 高接着性組成物 |
JPS6129540A (ja) * | 1984-07-20 | 1986-02-10 | 三井化学株式会社 | 積層フイルム |
KR920000173B1 (ko) * | 1986-10-09 | 1992-01-09 | 미쓰이세끼유 가가꾸고오교오 가부시끼가이샤 | 저결정성 프로필렌계 랜덤 공중합체 조성물, 그 제조방법 및 폴리프로필렌 복합 적층체 |
-
1987
- 1987-05-28 JP JP62130012A patent/JPH0729405B2/ja not_active Expired - Lifetime
-
1988
- 1988-05-24 US US07/197,957 patent/US5077123A/en not_active Expired - Lifetime
- 1988-05-25 DE DE8888304745T patent/DE3877624T2/de not_active Expired - Fee Related
- 1988-05-25 AT AT88304745T patent/ATE84748T1/de not_active IP Right Cessation
- 1988-05-25 AU AU16617/88A patent/AU606419B2/en not_active Ceased
- 1988-05-25 EP EP88304745A patent/EP0293187B1/en not_active Expired - Lifetime
- 1988-05-27 CA CA000567944A patent/CA1311998C/en not_active Expired - Fee Related
- 1988-05-27 NZ NZ224818A patent/NZ224818A/xx unknown
- 1988-05-28 CN CN88103178A patent/CN1019959C/zh not_active Expired - Fee Related
- 1988-05-28 KR KR1019880006359A patent/KR950012794B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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DE3877624T2 (de) | 1993-08-12 |
KR950012794B1 (ko) | 1995-10-21 |
JPS63295252A (ja) | 1988-12-01 |
AU1661788A (en) | 1988-12-01 |
US5077123A (en) | 1991-12-31 |
EP0293187B1 (en) | 1993-01-20 |
AU606419B2 (en) | 1991-02-07 |
CA1311998C (en) | 1992-12-29 |
CN88103178A (zh) | 1988-12-28 |
EP0293187A2 (en) | 1988-11-30 |
NZ224818A (en) | 1990-06-26 |
ATE84748T1 (de) | 1993-02-15 |
KR880013694A (ko) | 1988-12-21 |
EP0293187A3 (en) | 1990-01-31 |
JPH0729405B2 (ja) | 1995-04-05 |
DE3877624D1 (de) | 1993-03-04 |
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